Dithiocarbimates from Sulfonamides, Part 2: Preparation and X-Ray Crystal Structures o f (PPh4)2[Ni(S2C = N —S 0 2—Ph)2] and (PPh4)2[Ni(S2C = N —S 0 2—C6H4—CI)2] * 2 H20

Abstract

Abstract By reaction of K2[S2CNSO2C6H5] · 2H2O and K2[S2CNSO2C6H4Cl] · 2H2O, respectively, with Ni(CH3COO)2 · 4H2O the complex anions [Ni(S2C = N-(SO2-C6H5)2]2- and [Ni(S2C = N-SO2-C6H4-Cl)2]2- are formed and have been isolated in form of their (PPh4) salts. (PPh4)2[Ni(S2C = N-SO2-Ph)2] crystallizes monoclinicly. space group P21/a with a = 19.081(4), b = 9.106(1), c = 17.630(4) Å and β = 113.42(6)° with Z = 2. (PPh4)2[Ni(S2C = N-SO2-C6H4-Cl)2] · 2H2O crystallizes triclinicly, and the non-standard setting Cl has been choosen with a = 15.732(3), b = 22.509(4), c = 9.521(1) Å , ɑ = 96.30(6), β = 117.57(9), γ = 88.93(5)° and Z = 2. Within the complex anions nickel has the site-symmetry 1 and is coordinated by four sulfur atoms with Ni-S mean = 2.198 Å. The Ni(S2C = N-SO)2 units are essentially planar in both systems. This planarity gives rise to conjugation effects involving the SO2 group and the π-system of S2C = N - as well as the lone pair on N.